A Unifying model of strategic network formation

Documento de trabajo

Photochemical electron transfer at fixed distance : a synthetic model of the photosynthetic primary process

A series of meso-phenyloctamethylporphyrins covalently bonded at the 4'phenyl position to quinones via rigid bicyclo[2.2.2]octane spacers were synthesized for the study of the dependence of electron transfer reaction rate on solvent, distance, temperature, and energy gap. A general and convergent synthesis was developed based on the condensation of ac-biladienes with masked quinonespacer-benzaldehydes. From picosecond fluorescence spectroscopy emission lifetimes were measured in seven solvents of varying polarity. Rate constants were determined to vary from 5.0x10⁹sec^-1 in N,N-dimethylformamide to 1.15x10¹⁰ Sec^-1 in benzene, and were observed to rise at most by about a factor of three with decreasing solvent polarity. Experiments at low temperature in 2-MTHF glass (77K) revealed fast, nearly temperature-independent electron transfer characterized by non-exponential fluorescence decays, in contrast to monophasic behavior in fluid solution at 298K. This example evidently represents the first photosynthetic model system not based on proteins to display nearly temperature-independent electron transfer at high temperatures (nuclear tunneling). Low temperatures appear to freeze out the rotational motion of the chromophores, and the observed nonexponential fluorescence decays may be explained as a result of electron transfer from an ensemble of rotational conformations. The nonexponentiality demonstrates the sensitivity of the electron transfer rate to the precise magnitude of the electronic matrix element, which supports the expectation that electron transfer is nonadiabatic in this system. The addition of a second bicyclooctane moiety (15 Å vs. 18 Å edge-to-edge between porphyrin and quinone) reduces the transfer rate by at least a factor of 500-1500. Porphyrinquinones with variously substituted quinones allowed an examination of the dependence of the electron transfer rate constant κ_ET on reaction driving force. The classical trend of increasing rate versus increasing exothermicity occurs from 0.7 eV≤ |ΔG^0'(R)| ≤ 1.0 eV until a maximum is reached (κ_ET = 3 x 10⁸ sec^-1 rising to 1.15 x 10¹⁰ sec^-1 in acetonitrile). The rate remains insensitive to ΔG⁰ for ~ 300 mV from 1.0 eV≤ |ΔG^0’(R)| ≤ 1.3 eV, and then slightly decreases in the most exothermic case studied (cyanoquinone, κ_ET = 5 x 10⁹ sec^-1).

Tsunamis - a model of their generation and propagation

A general solution is presented for water waves generated by an arbitrary movement of the bed (in space and time) in a two-dimensional fluid domain with a uniform depth. The integral solution which is developed is based on a linearized approximation to the complete (nonlinear) set of governing equations. The general solution is evaluated for the specific case of a uniform upthrust or downthrow of a block section of the bed; two time-displacement histories of the bed movement are considered.

An integral solution (based on a linear theory) is also developed for a three-dimensional fluid domain of uniform depth for a class of bed movements which are axially symmetric. The integral solution is evaluated for the specific case of a block upthrust or downthrow of a section of the bed, circular in planform, with a time-displacement history identical to one of the motions used in the two-dimensional model.

Since the linear solutions are developed from a linearized approximation of the complete nonlinear description of wave behavior, the applicability of these solutions is investigated. Two types of non-linear effects are found which limit the applicability of the linear theory: (1) large nonlinear effects which occur in the region of generation during the bed movement, and (2) the gradual growth of nonlinear effects during wave propagation.

A model of wave behavior, which includes, in an approximate manner, both linear and nonlinear effects is presented for computing wave profiles after the linear theory has become invalid due to the growth of nonlinearities during wave propagation.

An experimental program has been conducted to confirm both the linear model for the two-dimensional fluid domain and the strategy suggested for determining wave profiles during propagation after the linear theory becomes invalid. The effect of a more general time-displacement history of the moving bed than those employed in the theoretical models is also investigated experimentally.

The linear theory is found to accurately approximate the wave behavior in the region of generation whenever the total displacement of the bed is much less than the water depth. Curves are developed and confirmed by the experiments which predict gross features of the lead wave propagating from the region of generation once the values of certain nondimensional parameters (which characterize the generation process) are known. For example, the maximum amplitude of the lead wave propagating from the region of generation has been found to never exceed approximately one-half of the total bed displacement. The gross features of the tsunami resulting from the Alaskan earthquake of 27 March 1964 can be estimated from the results of this study.

In Vitro Surfactant and Perfluorocarbon Aerosol Deposition in a Neonatal Physical Model of the Upper Conducting Airways

Objective: Aerosol delivery holds potential to release surfactant or perfluorocarbon (PFC) to the lungs of neonates with respiratory distress syndrome with minimal airway manipulation. Nevertheless, lung deposition in neonates tends to be very low due to extremely low lung volumes, narrow airways and high respiratory rates. In the present study, the feasibility of enhancing lung deposition by intracorporeal delivery of aerosols was investigated using a physical model of neonatal conducting airways. Methods: The main characteristics of the surfactant and PFC aerosols produced by a nebulization system, including the distal air pressure and air flow rate, liquid flow rate and mass median aerodynamic diameter (MMAD), were measured at different driving pressures (4-7 bar). Then, a three-dimensional model of the upper conducting airways of a neonate was manufactured by rapid prototyping and a deposition study was conducted. Results: The nebulization system produced relatively large amounts of aerosol ranging between 0.3 +/- 0.0 ml/min for surfactant at a driving pressure of 4 bar, and 2.0 +/- 0.1 ml/min for distilled water (H(2)Od) at 6 bar, with MMADs between 2.61 +/- 0.1 mu m for PFD at 7 bar and 10.18 +/- 0.4 mu m for FC-75 at 6 bar. The deposition study showed that for surfactant and H(2)Od aerosols, the highest percentage of the aerosolized mass (similar to 65%) was collected beyond the third generation of branching in the airway model. The use of this delivery system in combination with continuous positive airway pressure set at 5 cmH(2)O only increased total airway pressure by 1.59 cmH(2)O at the highest driving pressure (7 bar). Conclusion: This aerosol generating system has the potential to deliver relatively large amounts of surfactant and PFC beyond the third generation of branching in a neonatal airway model with minimal alteration of pre-set respiratory support.

Morphofunctional changes in a rat model of Parkinson's disease - Effects of neurotrophic factors administration

255 p.

Cytokine pathway disruption in a mouse model of schizophrenia induced by Munc18-1a overexpression in the brain

Background: An accumulating body of evidence points to the significance of neuroinflammation and immunogenetics in schizophrenia, and an imbalance of cytokines in the central nervous system (CNS) has been suggested to be associated with the disorder. Munc18-overexpressing mice (Munc18-OE) have provided a model for the study of the alterations that may underlie the symptoms of subjects with schizophrenia. The aim of the present study was to elucidate the involvement of neuroinflammation and cytokine imbalance in this model. Methods: Cytokines were evaluated in the cortex and the striatum of Munc18-OE and wild-type (WT) mice by enzyme-linked immunosorbent assay (ELISA). Protein levels of specific microglia and macrophage, astrocytic and neuroinflammation markers were quantified by western blot in the cortex and the striatum of Munc18-OE and WT mice. Results: Each cytokine evaluated (Interferon-gamma (IFN-gamma), Tumor Necrosis Factor-alpha (TNF-alpha), Interleukin-2 (IL-2) and CCL2 chemokine) was present at higher levels in the striatum of Munc18-OE mice than WT. Cortical TNF-alpha and IL-2 levels were significantly lower in Munc18-OE mice than WT mice. The microglia and macrophage marker CD11b was lower in the cortexes of Munc18-OE mice than WT, but no differences were observed in the striatum. Glial Fibrillary Acidic Protein (GFAP) and Nuclear Factor-kappaB (NF-kappa B)p65 levels were not different between the groups. Interleukin-1beta (IL-1 beta) and IL-6 levels were beneath detection limits. Conclusions: The disrupted levels of cytokines detected in the brain of Munc18-OE mice was found to be similar to clinical reports and endorses study of this type for analysis of this aspect of the disorder. The lower CD11b expression in the cortex but not in the striatum of the Munc18-OE mice may reflect differences in physiological activity. The cytokine expression pattern observed in Munc18-OE mice is similar to a previously published model of schizophrenia caused by maternal immune activation. Together, these data suggest a possible role for an immune imbalance in this disorder.

A model of the pelagic ecossystem in the eastern tropical Pacific Ocean

English: Recent calls for a more holistic approach to fisheries management have motivated development of trophic mass-balance models of ecosystems that underlie fisheries production. We developed a model hypothesis of the pelagic ecosystem in the eastern tropical Pacific Ocean (ETP) to gain insight into the relationships among the various species in the system and to explore the ecological implications of alternative methods of harvesting tunas. We represented the biomasses of and fluxes between the principal elements in the ecosystem with Ecopath, and examined the ecosystem's dynamic, time-series behavior with Ecosim. We parameterized the model for 38 species or groups of species, and described the sources, justifications, assumptions, and revisions of our estimates of the various parameters, diet relations, fisheries landings, and fisheries discards in the model. We conducted sensitivity analyses with an intermediate version of the model, for both the Ecopath mass-balance and the dynamic trajectories predicted by Ecosim. The analysis showed that changes in the basic parameters for two components at middle trophic levels, Cephalopods and Auxis spp., exert the greatest influence on the system. When the Cephalopod Q/B and Auxis spp. P/B were altered from their initial values and the model was rebalanced, the trends of the biomass trajectories predicted by Ecosim were not sensitive, but the scaling was sensitive for several components. We described the review process the model was subjected to, which included reviews by the IATTC Purse-seine Bycatch Working Group and by a working group supported by the National Center for Ecological Analysis and Synthesis. We fitted the model to historical time series of catches per unit of effort and mortality rates for yellowfin and bigeye tunas in simulations that incorporated historical fishing effort and a climate driver to represent the effect of El Niño-Southern Oscillation-scale variation on the system. The model was designed to evaluate the possible ecological implications of fishing for tunas in various ways. We recognize that a model cannot possibly represent all the complexity of a pelagic ocean ecosystem, but we believe that the ETP model provides insight into the structure and function of the pelagic ETP. Spanish: Llamamientos recientes hacia un enfoque más holístico al ordenamiento de la pesca han motivado el desarrollo de modelos tróficos de balance de masas de los ecosistemas que sostienen la producción pesquera. Desarrollamos una hipótesis modelo del ecosistema pelágico en el Océano Pacífico oriental tropical (POT) con miras a mejorar los conocimientos de las relaciones entre las distintas especies en el sistema y explorar las implicaciones ecológicas de métodos alternativos de capturar atunes. Con Ecopath representamos las biomasas de los elementos principales en el ecosistema, y los flujos entre los mismos, y con Ecosim examinamos el comportamiento dinámico del ecosistema con el tiempo. Parametrizamos el modelo para 38 especies o grupos de especies (denominados “componentes” del modelo), y describimos las fuentes, justificaciones, supuestos, y revisiones de nuestras estimaciones de los distintos parámetros, relaciones basadas en dieta, capturas retenidas de las pesquerías, y descartes de las mismas en el modelo. Realizamos análisis de sensibilidad con una versión intermedia del modelo, para el balance de masas de Ecopath y las trayectorias dinámicas predichas por Ecosim también. El análisis demostró que cambios en los parámetros básicos para dos componentes en niveles tróficos medianos, Cefalópodos y Auxis spp., ejercieron la mayor influencia sobre el sistema. Cuando se alteraron el Q/B de los Cefalópodos y el P/B de los Auxis spp. de sus valores iniciales y se balanceó el modelo de nuevo, las tendencias de las trayectorias de la biomasa predichas por Ecosim no fueron sensibles, pero la escala fue sensible para varios componentes. Describimos el proceso de revisión al que fue sujeto el modelo, inclusive revisiones por el Grupo de Trabajo sobre Captura Incidental de la CIAT y un grupo de trabajo apoyado por el Centro Nacional para Síntesis y Análisis Ecológicos. Ajustamos el modelo a series de tiempo históricas de capturas por unidad de esfuerzo y tasas de mortalidad de atunes aleta amarilla y patudo en simulaciones que incorporaron esfuerzo de pesca histórico e impulsos climáticos para representar el efecto de variaciones a escala de El Niño-Oscilación del Sur sobre el sistema. El modelo fue diseñado para evaluar las posibles implicaciones ecológicas de la pesca atunera de varias formas. Reconocemos la imposibilidad de que el modelo represente toda la complejidad de un ecosistema oceánico pelágico, pero creemos que el modelo del POT mejora los conocimientos de la estructura y función del POT pelágico.